Cellulosic structure and method of producing same



Patented Aug. 8, 1939 UNITED STATES PATENT "OFFICE 7 2,188,338 cmunosrcs'raocrmm sun mono!" raonucmo sm Winfield Walter Heckert, vWilmington,Del, as-

signor to E. I. duPont dc Nemonrss: Company, Wilmington, Del, acorporation of Delaware No Drawing. Application May 20, 1937. Serial No.143,830

26 Claims.

This invention relates to the manufacture of cellulose derivativematerials and especially cellulose acetate materials, such as yarns,threads, filaments, fibers and the like or fabrics made therefrom, orother structures such as films,

10 on even date herewith.

Cellulose derivative materials, and particularly materials made fromcellulose esters such as cellulose acetate, have always presented dyeingdifficulties. The dyestufis and dyeing. processes commonly used forcoloring cellulose acetate products are very costly in comparison to thedyeing of other materials. Furthermore, a great many of the dyes whichwill dye other materials will not dye cellulose acetate. Likewise, thedyestufis developed for cellulose acetate generally are not suitable fordyeing other fibers. 1n dyeing. mixed fabrics or threads which containboth cellulose acetate fibers and fibers of other materials such aswool, cotton, regenerated cellulose. linen or silk, it has heretofore,therefore, been necessary to subject the thread to a plurality of dyeingoperations in which the different fibers are separately dyed withdifferent dyestuffs. Another phase of dyeing of cellulose acetatefabrics in which difliculty has frequently been encountered,particularly with respect to suitable ranges of color, is the dischargeprinting of these fabrics. For lack of a better solution, it has longbeen standard practice to overcome as much as possible these dyeingdifflculties, by saponifying the cellulose acetate materials until asurface of regenerated cellulose is secured even though suchsaponification tended to impair the strength and handle of the celluloseacetate materials.

It has now been found that by treating cellulose derivativm particularlycellulose esters such as cellulose acetate with certain materials, theformer will have an afiinity with all known dyestuffs. Cellulosederivative materials can, due to this remarkable discovery, be dyed withcheaper dyes and with less expensive procedures. The present inventionwill furthermore permit the union dyeing of mixed fabrics with a singledye in a single dyeing procedure, and will permit the ready dyeing ofcellulose derivatives with direct and other dischargeable dyes and thedischarging of these dyes for the production of print goods without,resorting to expensive and degrading saponification procedures.

It is therefore an object of the present invention to provide a methodfor the treatment of cellulose derivatives, particularly celluloseesters, which will impart thereto an afflnity for all dyestuffs.

It is a further object of this invention to produce 9. treated cellulosederivative and more specifically 9. treated cellulose ester which willhave an afiinity for all dyestuffs.

It is another object of this invention to provide a process for theincorporation of certain materials in cellulose derivatives and morespecifically cellulose esters whereby to impart .to said derivative orester an afiinity for all dyestuffs.

It is still another object of this invention to produce a cellulosederivative and more specifically a cellulose ester having embodiedtherein a material which imparts thereto an afiinity for all dyestuffs.

The objects of the invention may be accomplished in general by treatingcellulose derivative structures or by incorporating in cellulosederivative solutions, preferably prior to the formation of saidstructures, a polymeric amino alcohol ester of acrylic acid or of alphasubstitilted acrylic acid of the type disclosed in the copendingapplication of Jesse Harmon, Serial No. 21,810, filed May 16, 1935.

As examples of polymeric amino alcohol esters of acrylic acid or ofalpha substituted acrylic acid suitable for use in accordance with thepresent invention may be mentioned:

Beta-dimethylaminoethyl methacrylate Beta-diethylaminoethyl methacrylateBeta-dicyclohexylaminoethyl methacrylate Beta-di-n-butylaminoethylmethacrylate 2-aminocyclohexyl methacrylate Triethanolaminemonomethacrylate '2-(diethylamino) cyclohexyl methacrylate 1-(beta-methacrylyloxyethyl) piperidine i-(beta-methacrylyoxyethyl)morpholine The amino alcohol esters of acrylic acid or of alphasubstituted acrylic acid may be prepared by treating the monomeric aminoalcohol ester of acrylic acid or of alpha substituted acrylic acid witha stoichiometric equivalent amount of an acid, thesalt thus formed beingdissolved in water or other suitable solvent and'the resulting solutionsubjected to polymerizing conditions in the presence or absence ofpolymerization catalysts as disclosed in detail in the above-identifiedHarmon application.

To further illustrate" the preparation of a few of these aminoresins'the following examples are given.

EXAMPLE A.- -Beta-dimethulaminoethyl methaerg late A. Synthesis ofmonomer: A solution of 89 grams (1 mol) of beta-dimethylaminoethanol and400 grams (4 mols) of methyl methacrylate in 500 gra ns of dry benzenecontaining 30 grams of paraphenylenediamine is made up, heated in an oilbath under a 48" fractionating column fitted with a distilling headarranged for controlled reflux, and distilled until the moisture presentin the reagents is removed. As soon as all the water is oil, a solutionof 2 grams of metallicsodium in cc. of dry methanol is added dropwise tothe refluxing reaction mixture during the course of 6 hours, duringwhich time a benzenemethanol binary (boiling point 58 C.) is collectedat the head of the column. The distillation and collection of binary iscontinued until no more methanol is liberated, whereupon the reactionmixture is allowed to cool, filtered, and the excess methyl methacrylateremoved by fractional distillation under reduced pressure through a longcolumn, and the product distilledthrough a short column under reduced.pressure in an atmosphereof nitrogen. The yield of product boiling at62-65 C. at 6 mm. pressure is 59% of the theoretical, and analyzes 8.2%nitrogen,

whereas the calculated value for -betadimethylaminoethyl methacrylate is8.97

B. Polymerization of the monomer: Polymerization. is effected bydissolving the monomer in an equivalentamount of dilute acetic acid, diluting'with water to 10% monomer concentration, adding powdered benzoylperoxide (1% based on the monomer), and heating at 100 C. for 21 hours.The viscous polymericsalt solu- 40 tion obtained is diluted to 1.5%resin concentration, the solution poured into-five times its vol ume ofacetone, and the polymeric salt that pre cipitates, filtered, and.dried, is obtained as a white, water-soluble powder. The polymeric freebase may be obtained by heatingthepolymeric' salt at about 100- C. Theproduct thus obtained issoluble in water, alcohol, acetone, etc.,whereas the polymeric free base obtained by spontaneous polymerizationof monomer at room temperature without catalyst is insoluble in commonorganic solvents.

ExAurLn B.-B eta-diethylaminoethyl methae crylate This compound is madeby dissolving'li'l grams (1 mol) oi beta-diethylaminoethanol and 1400grams (4 mols) of methyl methacrylate in 300 grams of dry benzenecontaining 30 grams p-phenylene diamine, and heated in an oil bath under.a 48" tractionatin'g column fitted with. a

'7 ings with the bulk of the product and then distilling the ether underreduced pressure in an atmosphere of nitrogen. The monomeric ester isleft in the distilling glass as an almost colorless liquid whichpolymerizes spontaneously to a 7 tough, transparent, pale amber polymer.W en amasss allowed to stand at room temperataire or even at a lowertemperature, the polymer was insoluble in water and in the commonoxygenated organic solvents,'soluble in acetone.

Exmu: C.-Beta-dicyclohezylaminoethyl methacrylate A.Beta-dicyclohexylamino ethanol: Eighty grams (1 mol) of ethylenechlorhydrin is added during 20 minutes to 185 grams (1.02 mols) ofdicyclohexylamine maintained at C. The mixture'is stirred and heated inan oil bath at C. for 14 hours, at the end of which time the reactionmixture is allowed to cool, and an excess of 20% sodium hydroxidesolution added, the oil that forms is separated, washed with water,dried, and fractionally distilled in vacuo. The yield of product boilingat 156-163 C. at 6 mm. pressure is 48-50% of the theoretical. Theproduct has a neutral equivalent or 228.5, whereas the calculatedneutral equivalent of beta-dicyclohexylamino ethanol is 225.

B. Synthesis of monomer: Beta-dicyclohexylaminoethyl methacrylatemonomer is made by ester interchange between methyl methacrylate andbeta-dicyclohexvlamino ethanol by the technique described under ExampleA, and purified by the method described under Example B. The yield ofproduct boiling at l5 3-159 C. at 2 mm. pressure is 73% of thetheoretical. Analysis of the product shows it to contain 4.87% nitrogen,whereas the theoretical-nitrogen content of betadicyclohexylaminoethylmethacrylate is 4.8%.

C. Polymerization of monomer: Polymerization iseffected by adding anequivalent amount of hydrochloric acid to a weighed sample ofthemonomer, warming to dissolve the monomer, diluting with water to 10%monomer concentration, adding powdered benzoyl peroxide (1% based onthemonomer), and heating at 100, C. for 24 hours.

The free base polymer is recovered as an amorphous powder, from thepolymeric salt solution by adding thereto an excess of sodiumbicarbonate solution. The free' base polymer thus obtained is soluble inbenzene, toluene, mineral spirits, and in an excessof dilutehydrochloric or acetic acids, whereas free base polymer obtained by thespontaneous polymerization at or below room temperature without catalystis insoluble in acids and organic solvents. The free base poly-- merobtained from the polymericsalt is .compatible with oil modifiedpolyhydric alcoholpolycarboxylic acid resins, nitrocellulose andChina-wood oil. I,

Instead of simple polymers, interpolymers may be prepared, for instanceby reacting methyl methacrylate and methyl vinyl ketone in the presenceor ammonium hydroxide or reacting beta-cyclohexylaminoethyl methacrylatemonomer and beta-dimethylaminoethyl methacrylate monomer together undersuitable conditions. Other equivalent polymeric materials such ascopolymers may also be used;

In carrying out the instant invention, these polymers are incorporatedin the cellulose deriva-' tive material, such as cellulose acetate inany suitable manner, as for instance by dissolving'or dispersing thepolymer in the cellulose acetate spinning solution, or by dissolving ordispersing the polymer in a suitable solvent or dispersing mediumimpregnating the cellulose acetate material with this solution ordispersion and removin: the solvent or dispersing medium. I

In accordance with the preferred embodiment of the invention, it isdesirable to have the amino polymerpresent in the cellulose derivativestructure in the form of a salt prior to the dyeing thereof. This may beaccomplished by formation of the amino polymer salt prior to the inorother water-soluble mono-basic acid to the cellulose derivative solutiontogether with the amino polymer, or by treating the cellulose derivativethread or other structure with a dilute solution of the acid beforedyeing the same. The addition of an organic acid to the cellulosederivative solution modified with the amino polymer constitutes separateinvention and accordingly is claimed in copending application to IzardSerial No. 146,440, filed June 4, 1937.

Cellulose derivatives and specifically cellulose esters which have beentreated in accordance with the present invention are found tohave aparticularly improved afinity for the so-called direct dyes, acid" dyes,developed'- color dyes, chrome dyes and vat dyes.

As illustrative examples of the above mentioned classes of dyes forwhich the cellulose derivatives of the present invention have asatisfactory afiinity upon actual test may be mentioned:

Direct dyes ,Pontamine" Scarlet 13, color index 382.

Pontamine Blue RW, color index 512.

Also direct dyes having color index Nos. 518, 278, 533, 415, 365, 598,419, 326, 593 and 539.

Acid dyes Milling Red R Conc., color index 430.

Brilliant Milling Green B Conc., color index 667.

Monophyil Fast Blue -R (color index not known). I

Also acid dyes having color index Nos. 649, 31, 1088 and 307.

Developed color dyes (diazo dyes) Chrome dyes "Pontachrome" Blue R,color index 179.

"Pontachrome Green G (see above mentioned yearbook).

Du Pont Chromate Brown m, color index PI. 12.

Also chrome dyes having color 40, 299 and 302.

index Nos. 215,

Vat dyes Suliant'nrene Scarlet G Paste (see above tloned yearbook).

Ponsol Jade Green Double Paste, color index 1101.

"Ponsol" Blue GD Double Paste, color index 1113.

Also vat dyes having color index No.1095, as well as SulfanthreneScarlet G Paste.

Basic dyes having color index Nos.'922 and 749.

Basic substituted anthra'quinone dyestuffs, commonly used to dyeunmodified cellulose acetate rayon, such as Celanthrene Red Y,Celanthrene Fast Light Yellow, Celanthrene Sky Blue B,Celanthrene'Scarlet G, and Acetamine Orange The color index numberscited in the present specification are all taken from Rowes ColourIndex, Society of Dyers and Colorists, first edition, 1924.

The following examples are given to illustrate the principles of thisinvention, it being understood of course that the invention -is notlimited to these precise examples which are merely illustrative of theinvention.

' ExAuPLs I The beta-diethylaminoethyl methacrylate prepared accordingto Example B is dissolved in acetone and to this solution suflicientcellulose acetate is added to form a spinning solution containing 20%cellulose acetate, 4% polymer and 76% acetone. The solution spunelectrically, for example, in the method set forth in Formhals PatentNo. 1,975,504.

The yarn to be dyed is soaked in an aqueous bath containing 0.5% sodiumoleate soap and 0.5% sodium carbonate heated to from ID-80 C. for 15minutes. The yarn is rinsed with water and permitted to drain for a fewminutes, after which it is immersed in a dye bath. The aqueous dye bathis made up with 15 to 20% of Glaubers salt, 4% of acetic acid of 28%concentration, and with a sufliclent quantity of a direct cotton dye,color index No. 382, to give the requisite depth of shade and a 40:1ratio of liquor volume to the weight of the material. The yarn isentered into the lukewarm bath and turned frequently while thetemperature of the dye bath is raised to 85-90" C. and maintained therefor 15 minutes. Two further 4% additions of acetic acid (28%concentration) are now made, each followed by heating to 8090 C. for 15minutes, if necessary to obtain exhaustion of the dye bath. The dyedyarn is removed, rinsed and dried.

The yarn so produced has good physical properties and shows goodaffinity for the direct dyestui! above mentioned as well as other kindsand types of dyes.

Exnirtz If The resinous polymer prepared according to Example G abovewas dissolved in 5% acetic acid to the extent of 2% resin. The solutionwas heated to 60 C. and a small piece of cellulose acetate fabricimmersed in a solution where it was allowed to remain for about 5minutes. The fabric was removed, the excess solution drained therefromand then placed in a 5% ammonium hydroxide water bath at roomtemperature for 5 minutes. .At the end of this time the sample wasremoved, rinsed with water and dried at 40 G. The fabric so treatedshowed a remarkable :znpz'oveinent in affinity for direct dyestuffs ascompared with cellulose acetate which had not seen treated.

Examua: m

An interpolymer prepared by the condensation of 65% dicyclohexyl aminoethyl methacrylate monomer and 35% dimethyl amino ethyl methacrylatemonomer is dissolved in a mixture of ethylene dichloride and isopropylalcohol and into this solution cellulose acetate is dissolved to form asolution containing:

Parts by weight Cellulose acetate 15 Ethylene dichloride '70 IsopropylalcohoL, 30 The interpolymer 3 The solution is spun electrically in themanner described in U. S. Patent No. 1,975,504. A sample of the fibersso produced when dyed in the manner described under Example I showedgood affinity for direct dyes.

ExAMPLr: IV

sired depth of shade. The modified cellulose acetate taffeta is enteredinto the lukewarm bath which has a :1 ratio of liquor volume to the,

weight of the material; the temperature is raised to 80-90 C. andmaintained there for 15 minutes while frequently turning the taffeta.Then, two further 4% additions of acetic acid (28% concentration) aremade, each followed by heating at 80-90 C. for 15 minutes if necessary,to obtain exhaustion of the dye bath. The fabric is next removed fromthe dye bath, rinsed well, and entered into a diazotizing bath at atemperature of 18-24 C. and containing 3% sodium nitrite and 4% sulfuricacid. After a treatment of 20 minutes with occasional turning, thefabric is quickly but thoroughly rinsed with water and entered into adeveloping bath cooled to a temperature of 15-18 C. and containing 1% ofbetanaphthol as the developer and 0.5% sodium hydroxide. The fabric istreated with the diazotizing bath for a period of 20 minutes, then isrinsed employed and the color desired. Some dyes,-

when developed with beta-naphthol for example, give one color while withsome other developer such as p-toluylene diamine, an entirely differentcolor will result. v

EXAMPLE V Cellulose acetate fabric woven from cellulose acetate threadsmodified with beta-diethyiaminoethyl methacrylate in accordance with theprocedure outlined in Example I may be dyed with Pontachrome blue R,color index 179 as follows:

An aqueous dye bath is made up with 15 to 20% of Glaubers salt,'4% ofacetic acid of 28% concentration, and with a sufficient quantity ofchrome dye of color index No. 179 to give the desired shade and a 40:1ratio of liquor volume to the weight of the material. The thoroughlywetted' fabric is entered in this dye bath and turned for 10 minutes.During the course of the next 15 minutes, the temperature of the dyebath is gradually raised to 85-90 C. and dyeing continued at thattemperature for 30 minutes with frequent turning of the fabric. At theend of the 30 minutes, the fabric is lifted from the dye bath, 10%additional acetic acid is added to the dye liquid and the dyeingcontinued for 30 minutes. The fabric is then lifted from the dye bathand entered in a fresh aqueous bath containing 2% potassium dichromateand 4% formic acid. The fabric is entered into this bath at 70 C. whichis then heated to 85-90 C. for 90 minutes. The dyed fabric is withdrawn,rinsed thoroughly, squeezed out, and dried.

Exmrn VIlI To print a' red shade on a woven or knitted fabric containingthe cellulose derivative yarn modifled according to the invention, thefollowing procedure may be followed:

The British gum, dissolved in a little water, is mixed with Gum arabicsolution and more water added, after which the whole is boiled for 10minutes and made up to bulk.

ployed. In the roller printing method, the print ing roller consists ofan iron mandrel having an outer copper shell bearing an intagiioengravure of the design to be printed. Below the printing roller islocated a color box containing the printing paste. Between the color boxand the printing roller is placed a revolving brush whichpicks up theprinting paste and smears it in a promiscuous fashion over the surfaceof the printing roller. As the printing roller rotates, a doctor knifescrapes the printing paste cleanly from the plain surface portion,leaving only the engraved portions of the printing roller filled withthe printing paste. A pressure drum having a springy surface ispositioned above and in contact with the printing roller. The celluloseacetate fabric is. passed between the printing roller and the pressuredrum and becomes printed by being forced into the engraved portions ofthe printing roller carrying the printing paste.

Thickening Grams Highly torreiied corn starch (British gum)- 600 Gumarabic aqueous solution) 600 Water 800 "Total 2,000

Cellulose acetate fabric woven from cellulose acetate threads modifiedwith beta-diethylaminoethyl methacrylate in accordance with the procedure outlined in Example I may be dyed with Ponsol" Jade Green DoublePaste, color index 1101 in the following manner:

20 parts of the dye paste is mixed with parts of the followingcomposition:

Parts A boiled mixture comprising 700 parts gum tragacanth (6%) and 300parts British gum powder 550 190 parts Potassium carbonate 190 Dissolveat 170 F. cool to 140 F. and add:

. Parts Sodium sulfoxylate formaldehyde 160 Glycerine 50 Water The dyemixture is printed on the fabric, dried, aged for 4 to 6 minutes at'214"F. to 220 F.'in an air-free ager, after which it is oxidized for 2 to 3minutes at F. to 130 F. in the following bath:

Parts Sodium perbora'te 5 Water 1000 After oxidation the prints arerinsed, soaped lightly, rinsed and dried.

If desired this printing of the vat dye can be carried out on a modifiedcellulose acetate fabric, dyed with a readily dischargeable ground shadeby the use of a developed dye as above describedin Example IV.

The modified cellulose acetate fabric will be dyed readily to anydesired depth in this manner and any developed color will be readily.discharged.

If it is desired to get a white discharge of the developed color, ordirect color, the following procedure can be used:

A printing paste is prepared as follows:

Parts Zinc sulfoxylate formaldehyde conc 20 Dietbylene glycol 15 Water15 Gum tragacanth (6% solution) 50 The pastes are printed on thedischargeable ground of direct or developed dye, dried, aged for 4 to 6minutes at 214-220 F. in an air-free age; rinsed, soaped lightly ifdesired rinsed and In discharge printing, it is distinctly preferred toapply the zinc or sodium formaldehye sulfoxylate discharge agents in thepresence of a solvent or softening agent for the organic derivative ofcellulose. In this connection it is particularly advantageous touse amixture of zinc or sodium iormaldehyde sulfoxylate with zinc thiocyanateand optionally an additional solvent or swelling agent.

In all the above examples, unless otherwise specified, percentages arebased on the weight of the material being treated.

It will be apparent from the foregoing examples that these polymericamino nitrogen conlose acetate structures in many ways.

taining bodies may be incorporated in the cellu- If the resin isincorporated in the solution from which the cellulose acetate structureis formed, which is the preferred method, it is generally desirable toadd a higher concentration of resin to the solution, based on thecellulose acetate content, than is added to the bath in which thecellulose acetate materials are after-treated.

1 If the polymer is to be added to the spinning solution, concentrationsas high as 30% or even .more, based on the weight of the celluloseacetate presentmay be used. In general, however, I find thatconcentrations ranging from 5% up to about 20%, depending of course onthe effectiveness of the specific materials chosen, are suilicient formost purposes. While it is possible to increase the depth of dyeing bythe addition of still larger quantities of the polymer, the increaseddepth of dyeing is offset by weakening of the cellulose acetatestructure, so that from the practical standpoint, it is advisable to useno more resin in the cellulose acetate structure than is necessary toobtain the depth of color desired.

Where the polymer is to be added to the cellulose acetate thread or thelike by after-treatment, concentrations of polymer in the solution whichis impregnated in the cellulose acetate structure need beno morethanabout 10%. Very good results have been secured with as little as 1%and generally, it is not necessary to increase the concentration over 5%or 6%. It is preferred to select a resin which, in a solution composedof 20% polymer, 10% water, and 70% acetone at 25 C has a viscositybetween 25 and 300 centipoises and it is particularly preferred toselect a resin having aviscosity of between 50 and centipoises.

It is preferred of course to select a resin which will be soluble in asuitable solvent according to the process to be used. For instance,

if the material is to be incorporated in a cellulose,

acetate spinning solution, a resin should be selected which is solublein acetone, acetone-alcohol mixtures, or other solvent or solventmixture for cellulose acetate. In some cases, it is possible to useresins which are dispersed rather than dissolved in the spinningsolution.

In some instances, it may be desirable to incorporate the resin formingmaterial or the monomer in the cellulose acetate structure and to formthe resin in situ. This is a desirable procedure, especially where theresin to be used is insoluble in a suitable solvent, but where the resinforming materials or the monomeris solu-' ble in a suitable solvent.

If desired, the dye may be dissolved in the treating bath containing theamine polymer, the monomer or the resin forming materials and thecellulose derivative structure treated in a single bath. Also, the dyemay be incorporated in the cellulose derivative solution along with theamino polymer or the like and colored structures produced therefrom.

This invention is of primary interest in con nectionwith celluloseesters, and more particularly cellulose acetate although other celluloseesterssuch as cellulose propionate, cellulose butyrate and the like canbe produced or improved dyeing characteristics by incorporating thereinone or more of the resins or polymers referred to in this case. Quiteprobably, cellulose others. such as benzyl cellulose, ethyl cellulose,methyl cellulose, glycol cellulose, etc, whether in the form of threads,films or other form may be en dowed with improved dyeing properties whentreated in accordance with the teachings of this invention.- j

It is apparent that this invention considerably widens the range ofdyestuffs available for use with cellulose acetate and other celluloseesters. It enables the dyer to use'new classes of dyes which can beeasily applied, which are relatively cheap and which will produceuniform colors fast to light, washing, and other factors tending toaffect the color. Furthermore, since these resins areof high molecularweight, they are slow to diffuse from the fiber and since they aregenerally of film forming materials, they do not tend to weaken thefiber to the extent the fibers would be weakened by incorporatingtherein low molecular weight substances such as monomers Also, thesematerials have a further advantage for this use in that they-aredefinitely not volatile and water insoluble and therefore resist removalby heat or washing. 7

By means of this invention cellulose acetate threads may be mixed withwool, cotton, regenerated cellulose or the like and satisfactory dye.results secured with the desired class of dyes. Furthermore, fabricsmade from 100% cellulose acetate yarn are simply and inexpensively dyedwith the desired dyestuff and dischargeable pritnsting may be carriedout with very good resul Parts and proportions referred to are parts andproportions by weight unless otherwise specified.

Since it is obvious that many changes and modifications can be made inthe above described processes and products without departing from thenature and spirit of the invention, it is to be understood that theinvention is not to be limited except as set forth in the appendedclaims.

I claim:

1.. The process of imparting to an' organic cellulose derivativestructure an aflinity for dyestufi's which comprises uniting the saidstructure with a polymeric amino alcohol ester of an acid taken from thegroup consisting of acrylic acid and alpha substituted acrylic acid.

2. The process of imparting to a cellulose. es-

ter structure an afiinity for dyestuffs which comprises uniting the saidstructure with a polym'eric amino alcohol ester of an acid. taken fromthe group consisting of acrylic acid and alpha substituted acrylic acid.

3. The process of imparting to a cellulose acetate structure an afiinityfor dyestuffs which comprises uniting the said structure with apolymeric amino alcohol ester of an acid taken from the group consistingof acrylic acid and alpha substituted acrylic acid.

4. The process of imparting to an organic cellulose derivative structurean afilnity for dyestufi's which comprises uniting the said structurewith a salt of a polymeric amino alcohol ester of an acid taken from thegroup consisting of acrylic acid and alpha substituted acrylic acid.

5,. The process of imparting to a cellulose ester structure an affinityfor dyestuffs .whichcomprises uniting the said structure with a salt ofa polymeric amino alcohol ester of an acid. taken from the groupconsisting of acrylic acidand alpha substituted acrylic acid.

6. The-process of imparting to a cellulose acetate structure an affinityfor dyestuffs which comprises uniting the said structure with a salt ofa polymeric amino alcohol ester "of an acid acid . which comprisesembodying in said structure a polymeric amino. alcohol ester of an acidtaken from the group consisting'of acrylic acid and alpha substitutedacrylic acid.

8. The process of imparting to a cellulose ester structure an afilnityfor dyestuffs which comprises embodying in 'said structure a polymericamino alcohol ester of an acid taken fromthe group consisting of acrylicacid and alpha substituted acrylic acid.

9. The process of imparting to a cellulose acetate structure an affinityfor dyestuffs which comprises embodying in said structure a polymericamino alcohol ester of an acid taken from' the group consisting ofacrylic acid and alpha substituted acrylic acid.

10. In a process of forming an organic cellulose derivative articlehaving an afiinity forall dyestuffs the steps comprising em y in acellulose derivative composition a polymeric amino alcohol ester of anacid taken from the group consisting of' acrylicacid' and alphasubstituted acrylic acid','forming an article therefrom, and convertingsaid polymer to a salt.

11. In a process of forming a cellulose ester article having an aillnityfor all dyestuffs the steps comprising embodying in a cellulose estercomposition a polymeric amino alcohol ester of an acid taken from thegroup consisting of acrylic acid and alpha substituted acrylic acid,forming an article therefrom, and converting said polymer to a salt.

12. In a process of forming a cellulose acetate article having anafiinity forall dyestuffs the steps comprising embodying in a celluloseacetate composition a polymeric amino alcohol ester of an acid takenfrom the group consisting of acrylic acid and alpha substituted acrylicacid, forming an article therefrom, and converting said polymer to asalt.

13. An organic cellulose derivative structure containing a polymericamino alcohol ester of an acid taken from the group consisting ofacrylic acid and alpha substituted acrylic acid, and a dyestuff.

14. A cellulose ester structure containing a polymeric amino alcoholester of an acid taken from the group consisting of acrylic acid and'alpha substituted acrylic acid, and a dyestufi'.

15. A cellulose acetate structure containing a polymeric amino alcoholester of an acid taken from the group consisting of acrylic acid andalpha substituted acrylic acid, and a dyestufl.

16. An organic cellulose derivative structure containing a salt of apolymericamino alcohol ester of an acid taken from the group consistingof acrylic acid and alpha substituted acrylic acid, and .a dyestufif. va

17. A cellulose ester structure containing a salt of a polymeric aminoalcohol ester of an acid an organic cellulose derivative structure thesteps comprising uniting the said structure with a polymeric aminoalcohol ester of an acid taken from the group consisting of acrylic acidand alpha substituted acrylic acid, dyeing said structure with adischargeable dye, and discharging said dye with a discharging agent.

20. In a process for the discharge dyeing ot an organic cellulosederivative structure the steps comprising uniting the said structurewith a polymeric amino alcohol ester of an acid taken from the groupconsisting of acrylic acid and alpha substituted acrylic acid, dyeingsaid structure with a dischargeable dye, and discharging said dye with adischarging agent composed of a mixture of a sulfoxylate and athiocyanate.

21. In a process for the discharge dyeing of an organic cellulosederivative structure the steps comprising uniting the said structurewith a polymeric amino alcohol ester of an acid taken from the groupconsisting of acrylic acid and alpha substituted acrylic acid, dyeingsaid structure with a dischargeable dye, and discharging said dye with adischarging agent composed of zinc formaldehyde sulfoxylate.

22. A discharge-dyed organic cellulose derivative structure containing apolymeric amino alcohol ester of an acid taken from the group consistingof acrylic acid and alpha; substituted acrylic acid and a dischargeabledye.

23. A discharge-dyed organic cellulose derivativestructure containing apolymeric amino alcohol ester of. an acid taken from the groupconsisting of acrylic acid and alpha substituted acrylic acid, a groundcolor comprising a dischargeable dye, and a design of contrasting color.

24. A discharge-dyed organic cellulose derivative structure containing apolymeric amino alcohol ester of\ an acid taken from the groupconsisting of acrylic acid and alpha substituted acrylic acid, a groundcolor comprising a dischargeable dye, and a colorless design.

25. An organic cellulose derivative structure and a developed dyestufi.

WINFIEID WALTER,- mzcxna'r.

